CN101137345B - Hair coloring compositions for use in oxidative hair dyeing - Google Patents
Hair coloring compositions for use in oxidative hair dyeing Download PDFInfo
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- CN101137345B CN101137345B CN2006800079426A CN200680007942A CN101137345B CN 101137345 B CN101137345 B CN 101137345B CN 2006800079426 A CN2006800079426 A CN 2006800079426A CN 200680007942 A CN200680007942 A CN 200680007942A CN 101137345 B CN101137345 B CN 101137345B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/411—Aromatic amines, i.e. where the amino group is directly linked to the aromatic nucleus
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
Abstract
Hair dyeing compositions are provided which comprise at least one coupler selected from N-aryl-m-phenylenediamine derivatives, 2-substituted N-aryl-m-phenylenediamine derivatives, and N-aryl-m-diaminopyridine derivatives, in combination with and at least one diaminopyrazole primary intermediate.
Description
Invention field
The present invention relates to be used for the new compositions of oxidizing hair coloring.More particularly, the present invention relates to comprise the hair colouring compositions of the combination of at least a coupling agent and at least a diamino-pyrazole main intermediate.Said coupling agent is selected from diaminopyridine derivatives between N-aryl m-diaminobenzene. derivant, the substituted N-aryl of 2-m-diaminobenzene. derivant and N-aryl.The invention still further relates to and use these hair colouring compositions to come pigmented hair.
Background of invention
Chromotrichia is a kind of method that adopts the number of ways practice since ancient times and obtain.In modern times, the most widely used method that is used for pigmented hair is to utilize the chromotrichia system to come pigmented hair by the method for oxidative coloration.Said coloring hairs system use one or more and one or more combined oxidizing hair coloring agents of oxidant.
Modal is to use the combination of peroxide oxidant and one or more oxidizing hair coloring agents.Said oxidative hair dyeing agent normally can be diffused in the hair and comprise one or more main intermediate and the micromolecule of one or more coupling agents.In the method, use peroxide material such as hydrogen peroxide to activate micromolecular main intermediate, so that they and coupling agent reaction, the chemical compound of formation large-size in dry, thus make hair catch multiple color tones and color.
Multiple main intermediate and coupling agent coupling agent in above-mentioned oxidative hair dyeing system and compositions, have been used.In the middle of employed main intermediate; Can mention p-phenylenediamine (PPD) is arranged, to toluenediamine, para-aminophenol, 4-amino-3-methylphenol, and the coupling agent that can mention has resorcinol, 2-methylresorcinol, 3-amino-phenol and 5-amino-2-methyl phenol.Used dyestuff to produce most of tone based on p-phenylenediamine (PPD).
Be used for coloring hairs or painted compositions and need be and to institute's dyeing hair those of whole color fastness to be provided.Therefore, the hair dyes that contains the present composition should be able to be resisted by washing, sour antiperspirant and caused the fading of wearing and tearing.Another required characteristic is, above-mentioned composition with since the influence of sour antiperspirant and on purple or blue direction coloured atomic little change show to have color fastness.The above-mentioned composition that especially need have above-mentioned improvement color fastness characteristic can or be coloured to purple or blueness with coloring hairs, or the chromophore in purple or the blue color spectrum is offered the hair dyes product composition.
Summary of the invention
The present invention relates to hair colouring compositions, said compositions comprises:
(a) at least a coupling agent, said coupling agent are selected from the group of being made up of the following compounds that meets chemical formula (1), chemical formula (1-B) and chemical formula (1-C) structure:
Chemical formula (1)
Wherein R is the part that is selected from chemical formula (2), (3) or (4):
R wherein
1, R
2, R
3, R
4And R
5Be selected from the group of forming by following groups independently of one another: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group;
Chemical formula (1-B)
R wherein
1Be aromatic ring; It is selected from the group of being made up of following groups: phenyl with have one or more heteroatomic 5 yuan or 6 yuan of heteroaryls; Said hetero atom is selected from O, S or N; Wherein said aromatic ring is unsubstituted or by one or more substituent groups replacements, said substituent group is selected from the group of being made up of following groups: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group;
Wherein R and R
2Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl and C
2-C
5The dihydroxy alkyl; With
Wherein Z is selected from the group of being made up of following groups: C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl, C
2-C
5Dihydroxy alkyl, C
1-C
5Aminoalkyl and C
1-C
5The methoxyl group alkyl; With
Chemical formula (1-C)
R wherein
1Be aromatic ring; It is selected from the group of being made up of following groups: phenyl with have one or more heteroatomic 5 yuan or 6 yuan of heteroaryls; Said hetero atom is selected from O, S or N; Wherein said aromatic ring is unsubstituted or by one or more substituent groups replacements, said substituent group is selected from the group of being made up of following groups: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group;
Wherein R and R
2Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl and C
2-C
5The dihydroxy alkyl; With
Wherein any is a nitrogen among A, B, X and the Y, and residual A, B, X and Y are carbon;
(b) at least a main intermediate with chemical formula (5) structure:
R wherein
6And R
7Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
4Alkyl, C
2-C
4Hydroxyalkyl, benzyl and phenyl; With
R wherein
8Be selected from the group of forming by following groups: hydrogen, C
1-C
4Alkyl and C
2-C
4Hydroxyalkyl;
Or the water soluble salt of their physiology permission; With
(c) carrier that suits.
These novel hair colouring compositions are used for to hair painted that dyestuff wherein can be by the good picked-up of hair being provided, and tone or the color that keeps stable in a long time is provided.Said new compositions can be used for coloring hairs to give color or tone, especially purple or blueness.Said color or tone have good Washing and good selectivity, and when contacting with light, shampoo or sour antiperspirant, significant change can not take place.Hair colouring compositions of the present invention can be used for to the hair dyes product composition purple or blue chromophore being provided, so as to adjusting the tone of the hair dyes of being given by the said goods compositions.
Detailed Description Of The Invention
Although this description is drawn a conclusion to particularly point out and clearly to require protection claims of the present invention, it is believed that through following explanation and can understand the present invention better.
Term used herein " hair colouring compositions " (also be called in this article following synonym: hair dye composition, hair coloring compositions or hair dyes lotion) is meant the compositions that before mixing with reagent composition, comprises oxidative dyestuff, comprises chemical compound as herein described.
Term " reagent composition " (also being called oxidizing agent composition or peroxide compositions in this article) is meant the compositions that before mixing with hair colouring compositions, comprises oxidant.
The term of interchangeable use " hair dyes product " or " hair dyes system " (being also referred to as coloring hairs system, coloring hairs product or chromotrichia system) are meant the combination of hair colouring compositions and reagent composition before mixing, and comprise conditioner product and operation instructions.The said goods or system provide like the cover box with packaged form usually.
Term " coloring hairs product composition " is meant through hair colouring compositions and reagent composition are mixed the compositions that forms.
Term " carrier " (or vehicle or substrate) is meant the combination that except that activating agent (the for example oxidative hair dyestuff in the hair colouring compositions), is included in the composition in the compositions.
Except as otherwise noted, only if indicated the other unit radix, all percentage ratios all by weight.
Hair colouring compositions
Hair colouring compositions of the present invention comprises (a) at least a coupling agent and at least a combination with diamino-pyrazole main intermediate of chemical formula (5) structure.Said coupling agent is selected from the N-aryl m-diaminobenzene. derivant of (1) structure that has chemical formula, 2-with chemical formula (1-B) structure and replaces N-aryl m-diaminobenzene. derivant and have diaminopyridine derivatives between the N-aryl of chemical formula (1-C) structure.
A.
Coupling agent
1.
N-aryl m-diaminobenzene. derivant with chemical formula (1) structure
In one embodiment of the invention, said hair colouring compositions comprises at least a coupling agent.Said coupling agent is selected from the N-aryl m-diaminobenzene. derivant that meets chemical formula (1) structure:
Wherein R is the part that is selected from chemical formula (2), (3) or (4):
R wherein
1, R
2, R
3, R
4And R
5Be selected from the group of forming by following groups independently of one another: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group.
For example; The N-aryl m-diaminobenzene. derivant that meets chemical formula (1) structure is to be selected from the group of being made up of following coupling agent chemical compound: N-phenyl-benzene-1; 3-diamidogen, N-(4-amino-phenyl)-benzene-1,3-diamidogen, 4-methoxyphenyl-(3-amino-phenyl)-amine and 3-methoxyphenyl-(3-amino-phenyl)-amine.
Can according to following reaction sequence, the coupling agent chemical compound that preparation has chemical formula (1) structure, wherein R such as preceding text define.
In this reaction, 1-bromo-3-Nitrobenzol (6) is R-NH with chemical formula
2The via palladium-catalyzed amination of arylamine (7) generate N-aryl meta nitro aniline (8), it generates N-aryl m-diaminobenzene. (1) through hydrogenation.
Use above-mentioned synthetic method, prepare following two embodiment coupling agent chemical compounds.
Synthetic embodiment 1
Synthetic 4-methoxyphenyl-(3-amino-phenyl)-amine
With 1-bromo-3-Nitrobenzol (6) (2mmol, 0.40g), P-nethoxyaniline (7) (2.4mmol, 0.30g), sodium tert-butoxide (2.8mmol, 0.26g), Pd
2(dba)
3(10%mol, 0.18g), (10%mol, 0.13g) (4mL, the suspension in 0.5M) is at 100 ℃ at toluene for BINAP
1Under stirred 18 hours.Mixture is cooled to room temperature, on kieselguhr, filters, and with ethyl acetate (3 * 5mL) washings.(Na is used in 3 * 5mL) washings with the organic layer water that merges
2SO
4Drying concentrates, and purification (silica gel, 100% hexane), obtains yellowish-brown powder (8) (0.1g, 23% yield):
1H NMR (DMSO-d
6) δ 8.46 (s, 1H), 7.61 (t, 1H), 7.49 (d, 1H), 7.40 (t, 1H), 7.25 (d, 1H), 7.15 (d, 2H), 6.95 (d, 2H), 3.80 (s, 3H).In MeOH (20mL) with Pd/C (10%, 0.01g) in the H of 0.4MPa (60psi)
2Following to (8) (0.1g) hydrogenation 2 hours, obtain 4-methoxyphenyl-(3-amino-phenyl)-amine (1) (0.04g, 45% yield):
1H NMR (DMSO-d
6) δ 7.51 (s, 1H), 7.00 (d, 2H), 6.82 (d, 3H), 6.20 (s, 1H), 6.12 (s, 1H), 5.99 (d, 1H), 4.48 (s, 2H), 3.75 (s, 3H); MS 214 (M
+), 199,182,169,154,107,91,85,65.
1:R.A.Singer, J.P.Dadighi and S.L.Buchwald, J.Am.Chem.Soc., volume was the 213rd page in 1998 the 120th.
Synthetic embodiment 2
Synthetic 3-methoxyphenyl-(3-amino-phenyl)-amine
Method according to described in the synthetic embodiment 1 of preceding text prepares chemical compound 3-methoxyphenyl-(3-amino-phenyl)-amine, substitutes P-nethoxyaniline as reactant (7) with m-anisidine.The characteristic of product is shown in following parameter:
1H NMR (DMSO-d
6) δ 7.93 (s, 1H), 7.16 (d, 1H), 6.90 (t, 1H), 6.63 (d, 2H), 6.43 (t, 2H), 6.30 (d, 1H), 6.13 (d, 1H), 5.23 (s, 2H), 3.70 (s, 3H); MS 214 (M
+), 213,198,182,169,154,143,127,107,91,85,65.
2.
2-with chemical formula (1-B) structure replaces N-aryl m-diaminobenzene. derivant
In another embodiment of the invention, said hair colouring compositions comprises at least a coupling agent.Said coupling agent is selected from the 2-that meets chemical formula (1-B) structure and replaces N-aryl m-diaminobenzene. derivant:
R wherein
1Be aromatic ring; It is selected from the group of being made up of following groups: phenyl with have one or more heteroatomic 5 yuan or 6 yuan of heteroaryls; Said hetero atom is selected from O, S or N; And wherein said aromatic ring is unsubstituted or by one or more substituent groups replacements, said substituent group is selected from the group of being made up of following groups: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group;
Wherein R and R
2Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl and C
2-C
5The dihydroxy alkyl; With
Wherein Z is selected from the group of being made up of following groups: C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl, C
2-C
5Dihydroxy alkyl, C
1-C
5Aminoalkyl and C
1-C
5The methoxyl group alkyl.
For example; The 2-replacement N-aryl m-diaminobenzene. derivant that meets chemical formula (1-B) structure is to be selected from the group of being made up of following coupling agent chemical compound: N2-(3-amino-2-methyl-phenyl)-pyridine-2,5-diamidogen, N-(4-amino-phenyl)-2-methyl-benzene-1,3-diamidogen, N-(4-amino-phenyl)-N '-ethyl-2-methyl-benzene-1; 3-diamidogen, 2-[2-amino-6-(4-amino-phenyl amino)-phenyl]-ethanol, 2-[[4-(3-amino-2-methyl-phenyl amino)-phenyl]-(2-hydroxyethyl)-amino]-ethanol, 2-methyl-N-(4-pyrrolidine-1-base-phenyl)-benzene-1; 3-diamidogen, 2-amino methyl-N-(4-amino-phenyl)-benzene-1,3-diamidogen, [2-amino-6-(4-amino-phenyl amino)-phenyl]-methanol, N-(4-amino-phenyl)-2-methoxy-benzene-1,3-diamidogen, N1-[3-amino-2-(amino methyl) phenyl] benzene-1; 4-diamidogen, N1-[3-amino-2-(cyano methyl) phenyl] benzene-1; 4-diamidogen, N1-(3-amino-2-ethenylphenyl) benzene-1,4-diamidogen, N1-[3-amino-2-(hydroxymethyl) phenyl] benzene-1,4-diamidogen, 2-[N-(3-aminophenyl)-N-(4-aminophenyl) amino] ethanol, N1-[3-amino-2-(1-hydroxyethyl) phenyl] benzene-1; 4-diamidogen, N1; N1-two (2-hydroxyethyl)-N4-(3 '-aminophenyl)-1,4-diaminobenzene, N1-{3-amino-2-[(E)-and third-1-thiazolinyl] phenyl } benzene-1,4-diamidogen, 1-(4-aminophenyl)-1; 2; 3,4-tetrahydroquinoline-5-amine, 1-(4-aminophenyl) indoline-4-amine, N1-(1,2-EEDQ-5-yl) benzene-1; 4-diamidogen and N1-(indoline-4-yl) benzene-1, the 4-diamidogen.
Can according to the reactions order, the coupling agent chemical compound that preparation has chemical formula (1-B) structure.
3.
Has diaminopyridine derivatives between the N-aryl of chemical formula (1-C) structure
In another embodiment of the invention, said hair colouring compositions also comprises at least a coupling agent.Said coupling agent is selected from diaminopyridine derivatives between the N-aryl of (1-C) structure that has chemical formula:
R wherein
1Be aromatic ring; It is selected from the group of being made up of following groups: phenyl with have one or more heteroatomic 5 yuan or 6 yuan of heteroaryls; Said hetero atom is selected from O, S or N; And wherein said aromatic ring is unsubstituted or by one or more substituent groups replacements, said substituent group is selected from the group of being made up of following groups: hydrogen, halogen, hydroxyl, amino, C
1-C
4Alkyl or haloalkyl, C
1-C
4Alkoxyl or halogenated alkoxy and itrile group;
Wherein R and R
2Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
5Alkyl, C
1-C
5Monohydroxy alkyl and C
2-C
5The dihydroxy alkyl; With
Wherein any is a nitrogen among A, B, X and the Y, and residual A, B, X and Y are carbon.
For example, meet that diaminopyridine derivatives is to be selected from the group of being made up of following coupling agent chemical compound: N-(4-amino-phenyl)-pyridine-2 between the N-aryl of chemical formula (1-C) structure, 6-diamidogen, N-(5-amino-pyridine-2-yl) pyridine-2; 6-diamidogen, N-(5-aminopyridine-2-yl) benzene-1,3-diamidogen, N-(4-pyrrolidine-1-base-phenyl)-pyridine-2,6-diamidogen, N-(4-amino-phenyl)-N '-methyl-pyridine-2; 6-diamidogen, 2-[4-(6-methylamino-pyridine-2-base is amino)-phenyl amino]-ethanol, 2-[6-(4-amino-phenyl amino)-pyridine-2-base is amino]-ethanol, N-(4-amino-phenyl)-N-methyl-pyridine-2,6-diamidogen, N-(1H-pyrroles-2-yl)-pyridine-2,6-diamidogen, N-(6-amino-pyridine-2-yl)-pyrimidine-2; 4,5, (5-amino-[1 for 6-tetramine, N-; 3,4] thiadiazoles-2-yl)-and pyridine-2,6-diamidogen, N3-(4-aminophenyl) pyridine-3; 5-diamidogen, N3-(4-aminophenyl)-N5-(2-hydroxyethyl) pyridine-3,5-diamidogen, N3-(thiazol-2-yl) pyridine-3,5-diamidogen, N2-(4-aminophenyl) pyridine-2; 4-diamidogen, N2-(4-aminophenyl)-5-chloropyridine-2,6-diamidogen, N2-(4-aminophenyl)-5-methoxypyridine-2,6-diamidogen, N3-(4-aminophenyl)-N3-picoline-3; 5-diamidogen, N3-(5-aminopyridine-2-yl) pyridine-3,5-diamidogen, N3-(4,5; 6-Triaminopyrimidine-2-yl) pyridine-3; 5-diamidogen, N2-(4-aminophenyl)-N2-picoline-2,4-diamidogen, N4-(4-aminophenyl)-N4-picoline-2,4-diamidogen, N2-(4-aminophenyl)-3-chloropyridine-2; 6-diamidogen and N2-(4-aminophenyl)-3-Methoxy Pyridine-2, the 6-diamidogen.
Can according to following reaction sequence, the coupling agent chemical compound that preparation has chemical formula (1-B) structure and chemical formula (1-C) structure:
In this reaction sequence, in the presence of sodium hydride, chemical compound 1 reacts in DMF with 1-fluoro-4-Nitrobenzol 2, obtains chemical compound 3.In methanol,, generate chemical compound 4 with hydrogen and Pd/C hydrogenated compound 3.
Use above-mentioned synthetic method, preparation the following example coupling agent chemical compound.
Synthetic embodiment 3
Synthetic N-(4-amino-phenyl)-pyridine-2, the 6-diamidogen
With 2, (9.2mmol, 1.0g) (9.2mmol 1.3g) is dissolved in the 10mL dry DMF 6-diamino-pyridine with 1-fluoro-4-Nitrobenzol.Agitating solution at ambient temperature, add simultaneously 95% sodium hydride (18.3mmol, 440mg).In 30 minutes, said solution becomes reddish black.At room temperature with said reactant mixture restir 20 hours.Said reactant mixture slowly is poured into and ices (25g) blended 25mL 10%NH
4In the Cl aqueous solution.With EtOAc (4 * 30mL) extraction obtained aqueous solutions.Use MgSO
4The dry organic facies that merges, and be concentrated into dried.Through rapid column chromatography, go up the remaining oil of purification at silica gel (EtOAc: hexane is 1: 2), obtain N2-(4-nitrobenzophenone) pyridine-2,6-diamidogen (1.6g, 76%) is the reddish orange crystal:
1HNMR (500MHz, CDCl
3) δ 8.19 (d, 2H, J=9.0Hz), 7.51 (d, 2H, J=9.0Hz), 7.42 (t, 1H, J=8.0Hz), 6.85 (s, 1H), 6.30 (d, 1H, J=8.0Hz), 6.16 (d, 1H, J=8.0Hz), 4.51 (s, 2H); MS m/z (relative intensity) 231 (M+1,100), 184 (100).With N2-(4-nitrobenzophenone) pyridine-2, the 6-diamidogen (2.6mmol, 0.6g) and 10%Pd/C (30mg) join in the 20mL test tube of being furnished with stirrer, being about to add MeOH (8mL) before, in said mixture, add dry ice (0.5g, CO then
2).0.6MPa (80psi) H is arranged in then suspension being put into
2Pressure vessel in.Said reactant mixture was stirred 3 hours.Said solution becomes colourless from yellow.Said reactant mixture is transferred in the 10mL syringe, and through the Acrodisc syringe filter, be filled in the round-bottomed flask that 100mL comprises 37%HCl aqueous solution (4mL).Solvent evaporated then, and with toluene and dehydrated alcohol (1: 1 mixture of 3 * 30mL) azeotropic to doing.Obtain pale powder shape product with quantitative yield:
1HNMR (500MHz, D
2O) δ 7.48 (t, 1H, J=14.0Hz), 7.25 (m, 4H), 6.13 (d, 1H, J=14.0Hz), 6.09 (d, 1H, J=14.0Hz); Ms m/z (relative intensity) 201 (M+1,100).
Also can according to following reaction sequence, the coupling agent chemical compound that preparation has chemical formula (1-B) structure and chemical formula (1-C) structure:
In this reaction sequence, chemical compound 6 replaces with the aromatics of chemical compound 5 in hot DMSO, generates chemical compound 7.In MeOH,, generate chemical compound 8 with hydrogen and Pd/C hydrogenated compound 7.
Use above-mentioned synthetic method, prepare following two embodiment coupling agent chemical compounds.
Synthetic embodiment 4
Synthetic N-(5-amino-pyridine-2-yl) pyridine-2, the 6-diamidogen
With 2, (9.2mmol, 1.0g) (4.6mmol 0.65g) is dissolved among the 6mL DMSO 6-diamino-pyridine with 2-fluoro-5-nitropyridine.Said solution was heated 18 hours down at 80 ℃.Said solution finally becomes dark red.Make said reactant mixture be cooled to room temperature, and (silicon dioxide, EtOAc: direct purification hexane=1: 3) obtain N through rapid column chromatography
2-(5-nitropyridine-2-yl) pyridine-2, the 6-diamidogen is red crystalline solid (0.21g, 20% yield):
1H NMR (500MHz, CDCl
3) δ 9.13 (d, 1H, J=3.0Hz), 8.36 (dd, 1H, J
1=3.0Hz, J
2=9.5Hz), 7.94 (d, 1H, J=9.5Hz), 7.66 (s, 1H), 7.46 (t, 1H, J=8.0Hz), 6.68 (d, 1H, J=8.0Hz), 6.23 (d, 1H, J=8.0Hz), 4.46 (s, 2H); Ms m/z (relative intensity) 232 (M+1,100), 186 (57).With said nitro compound (0.78mmol, 0.18g) and 10%Pd/C (20mg) join in the 20mL test tube of being furnished with stirrer, being about to add MeOH (7mL) before, in said mixture, add dry ice (0.5g) then.0.6MPa (80psi) H is arranged in then suspension being put into
2Pressure vessel in.Said reactant mixture was stirred 2 hours.Said solution becomes colourless from yellow.Said reactant mixture is transferred in the 10mL syringe,, be filled in the round-bottomed flask that 100mL comprises 37%HCl aqueous solution (4mL) then through the Acrodisc syringe filter.Solvent evaporated then, and with toluene and dehydrated alcohol (1: 1 mixture of 3 * 30mL) azeotropic to doing.Obtain the ecru powdery product with quantitative yield.
Synthetic embodiment 5
Synthetic N-(5-aminopyridine-2-yl) benzene-1, the 3-diamidogen
(2.8mmol, 0.30g) (0.92mmol 0.13g) is dissolved among the 6mL DMSO with 2-fluoro-5-nitropyridine with m-diaminobenzene..Said solution was heated 18 hours down at 80 ℃.Said solution finally becomes dark red.Make said reactant mixture be cooled to room temperature, and (silicon dioxide, EtOAc: direct purification hexane=1: 3) obtain N through rapid column chromatography
1-(5-nitropyridine-2-yl) benzene-1, the 3-diamidogen is red crystals chemical compound (0.19g, 89% yield):
1H NMR (500MHz, CDCl
3) δ 9.08 (d, 1H, J=2.5Hz), 8.24 (dd, 1H, J
1=2.5Hz, J
2=9.5Hz), 7.281 (s, 1H), 7.19 (t, 1H, J=8.0Hz), 6.82 (d, 1H, J=9.5Hz), 6.74 (s, 1H), 6.70 (d, 1H, J=8.0Hz), 6.56 (d, 1H, J=7.5Hz), 3.80 (br, 2H);
13C NMR (125MHz, CDCl
3) δ 159.91,148.05,146.93,139.09,137.15,133.59,130.77,112.80,112.66,109.13,106.67.With said nitro compound (0.43mmol, 0.10g) and 10%Pd/C (10mg) join in the 20mL test tube of being furnished with stirrer, being about to add MeOH (7mL) before, in said mixture, add dry ice (0.5g) then.0.6MPa (80psi) H is arranged in then suspension being put into
2Pressure vessel in.Said reactant mixture was stirred 2 hours.Said solution becomes colourless from yellow.Said reactant mixture is transferred in the 10mL syringe, and through the Acrodisc syringe filter, be filled in the round-bottomed flask that 100mL comprises 37%HCl aqueous solution (3mL).Solvent evaporated then, and with toluene and dehydrated alcohol (1: 1 mixture of 3 * 30mL) azeotropic to doing.Obtain the ecru powdery product with quantitative yield.
B. the main intermediate that has chemical formula (5) structure
Hair colouring compositions of the present invention also comprises the diamino-pyrazole main intermediate with chemical formula (5) structure of at least a and above-mentioned coupling agent combination:
R wherein
6And R
7Be selected from the group of forming by following groups independently of one another: hydrogen, C
1-C
4Alkyl, C
2-C
4Hydroxyalkyl, benzyl and phenyl; With
R wherein
8Be selected from the group of forming by following groups: hydrogen, C
1-C
4Alkyl and C
2-C
4Hydroxyalkyl; Or the water soluble salt of their physiology permission.
For example, the diamino-pyrazole main intermediate is 2-(4,5-diaminourea-pyrazol-1-yl)-alcohol cpd, the chemical compound that promptly has chemical formula (5) structure, wherein R
6Be hydroxyethyl, R
7And R
8Be hydrogen atom, and NR
7R
8Part is on 5.
Can pass through United States Patent (USP) 5,061, the method described in 289 prepares the diamino-pyrazole main intermediate of (5) structure that has chemical formula.
C.
Auxiliary main intermediate and auxiliary coupling agent
For the hair colouring compositions of this invention; Can use one or more N-aryl m-diaminobenzene. derivants, 2-to replace between N-aryl m-diaminobenzene. derivant and/or N-aryl diaminopyridine derivatives as coupling agent, with one or more diamino-pyrazole main intermediate combinations.If desired, hair coloring compositions of the present invention also can comprise one or more auxiliary main intermediate chemical compounds and/or one or more auxiliary coupling immunomodulator compounds.
Suitable known main intermediate for example comprises: suitable known main intermediate for example comprises:
The p-phenylene diamine derivative, for example: benzene-1,4-diamidogen (being commonly referred to p-phenylenediamine (PPD)), 2-methyl-benzene-1; 4-diamidogen, 2-chloro-benzene-1,4-diamidogen, N-phenyl-benzene-1,4-diamidogen, N-(2-ethoxyethyl group) benzene-1; 4-diamidogen, 2-[(4-amino-phenyl)-(2-hydroxyethyl)-amino]-ethanol (being commonly referred to N, N-two (2-hydroxyethyl)-p-phenylenediamine (PPD)), (2,5-diaminourea-phenyl)-methanol, 1-(2; 5-diaminourea-phenyl)-and ethanol, 2-(2,5-diaminourea-phenyl)-ethanol, N-(4-aminophenyl) benzene-1,4-diamidogen, 2; 6-dimethyl-benzene-1,4-diamidogen, 2-isopropyl-benzene-1,4-diamidogen, 1-[(4-aminophenyl) amino]-propan-2-ol, 2-propyl group-benzene-1; 4-diamidogen, 1,3-two [(4-aminophenyl) (2-hydroxyethyl) amino] propan-2-ol, N
4, N
4, 2-trimethylbenzene-1,4-diamidogen, 2-methoxyl group-benzene-1,4-diamidogen, 1-(2; The 5-diamino-phenyl) second-1,2-glycol, 2,3-dimethyl-benzene-1,4-diamidogen, N-(4-amino-3-hydroxyl-phenyl)-acetamide, 2; 6-diethylbenzene-1,4-diamidogen, 2,5-dimethyl benzene-1,4-diamidogen, 2-thiophene-2-base benzene-1; 4-diamidogen, 2-thiene-3-yl-benzene-1,4-diamidogen, 2-pyridin-3-yl benzene-1,4-diamidogen, 1,1 '-xenyl-2; 5-diamidogen, 2-(methoxy) benzene-1,4-diamidogen, 2-(amino methyl) benzene-1,4-diamidogen, 2-(2, the 5-diamino phenoxy) ethanol, [2-(2 for N-; The 5-diamino phenoxy) ethyl]-acetamide, N, N-dimethyl benzene-1,4-diamidogen, N; N-diethylbenzene-1,4-diamidogen, N, N-dipropyl benzene-1; 4-diamidogen, 2-[(4-aminophenyl) (ethyl) amino] ethanol, 2-[(4-amino-3-methyl-phenyl)-(2-hydroxyethyl)-amino]-ethanol, N-(2-methoxy ethyl)-benzene-1,4-diamidogen, 3-[(4-aminophenyl) amino] third-1-alcohol, 3-[(4-aminophenyl)-amino] the third-1,2-glycol, N-{4-[(4-aminophenyl) amino] butyl } benzene-1; 4-diamidogen and 2-[2-(2-{2-[(2, the 5-diamino-phenyl)-oxo] ethyoxyl } ethyoxyl) ethyoxyl] benzene-1, the 4-diamidogen;
P-aminophenol derivatives such as: 4 - aminophenol (often referred to as p-aminophenol), 4 - methyl-amino phenol, 4 - amino-3 - methylphenol, 4 - amino -2 - hydroxy methyl - phenol, 4 - amino -2 - methyl - phenol, 4 - amino -2 - [(2 - hydroxy-ethylamino) - methyl] - phenol, 4 - amino -2 - methoxy-methyl phenol, 5 - amino - 2 - hydroxybenzoic acid, 1 - (5 - amino-2 - hydroxyphenyl) ethylene-1 ,2 - diol, 4 - amino -2 - (2 - hydroxyethyl) phenol, 4 - amino-3 - ( Kong methyl) phenol, 4 - Amino - 3 - fluoro-phenol, 4 - amino -2 - (aminomethyl) - phenol and 4 - amino-2 - fluoro - phenol;
O-aminophenol derivatives; For example: 2-amino-phenol (being commonly referred to o-aminophenol), 2,4-diaminophenol, 2-amino-5-methylphenol, 2-amino-6-methyl-phenol, N-(4-amino-3-hydroxyl-phenyl)-acetamide and 2-amino-4-methyl-phenol; With
Hete rocyclic derivatives, for example: pyrimidine-2,4,5,6-tetramine (being commonly referred to 2,4,5, the 6-4-aminopyridine), 1-methyl isophthalic acid H-pyrazoles-4,5-diamidogen, 2-(4,5-diaminostilbene H-pyrazol-1-yl) ethanol, N
2, N
2-lutidines-2,5-diamidogen, 2-[(3-amino-6-methoxy pyrimidine-2-yl) amino] ethanol, 6-methoxyl group-N
2-picoline-2,3-diamidogen, 2,5; 6-Triaminopyrimidine-4 (1H)-ketone, pyridine-2; 5-diamidogen, 1-isopropyl-1H-pyrazoles-4,5-diamidogen, 1-(4-methyl-benzyl)-1H-pyrazoles-4,5-diamidogen, 1-(benzyl)-1H-pyrazoles-4; 5-diamidogen and 1-(4-benzyl chloride base)-1H-pyrazoles-4, the 5-diamidogen.
Suitable known coupling agent comprises, for example:
Phenol, resorcinol and naphthol derivative, for example: naphthalene-1,7-diphenol, benzene-1,3-diphenol, 4-chlorobenzene-1,3-diphenol, naphthalene-1-phenol, 2-methyl naphthalene-1-phenol, naphthalene-1; 5-diphenol, naphthalene-2,7-diphenol, benzene-1,4-diphenol, 2-methylbenzene-1,3-diphenol, 7-amino-4-hydroxy-naphthalene-2-sulfonic acid, 2-isopropyl-5-methylphenol, 1,2; 3,4-tetrahydrochysene-naphthalene-1,5-diphenol, 2-chloro-benzene-1,3-diphenol, 4-hydroxyl-naphthalene-1-sulfonic acid, benzene-1; 2,3-triphenol, naphthalene-2,3-diphenol, 5-two chloro-2-methylbenzene-1,3-diphenol, 4; 6-dichloro-benzenes-1,3-diphenol and 2,3-dihydroxy-[1,4] naphthoquinone;
M-diaminobenzene., for example: 2,4-diaminophenol, benzene-1; 3-diamidogen, 2-(2, the 4-diamino phenoxy) ethanol, 2-[(3-aminophenyl)-(2-ethoxy) amino] ethanol, 2-methylbenzene-1, [[2-(2 for 3-diamidogen, 2-; The 4-diamino phenoxy) ethyl]-(2-ethoxy) amino] ethanol, 4-{3-[(2, the 4-diamino-phenyl) oxo] propoxyl group } benzene-1,3-diamidogen, 2-(2; 4-diaminourea-phenyl)-and ethanol, 2-(3-amino-4-methoxyl group-phenyl amino)-ethanol, 4-(2-amino-ethyoxyl)-benzene-1,3-diamidogen, (2,4-diaminourea-phenoxy group)-acetic acid, 2-[2; 4-diaminourea-5-(2-hydroxyl-ethyoxyl)-phenoxy group]-ethanol, 4-ethyoxyl-6-methyl-benzene-1,3-diamidogen, 2-(2,4-diaminourea-5-methyl-phenoxy group)-ethanol, 4; 6-dimethoxy-benzene-1,3-diamidogen, 2-[3-(the 2-hydroxyethyl is amino)-2-methyl-phenyl amino]-ethanol, 3-(2,4-diaminourea-phenoxy group)-third-1-alcohol, N-[3-(dimethylamino) phenyl] urea, 4-methoxyl group-6-methylbenzene-1; 3-diamidogen, 4-fluoro-6-methylbenzene-1; 3-diamidogen, 2-({ 3-[(2-hydroxyethyl) amino]-4,6-Dimethoxyphenyl }-amino) ethanol, 3-(2, the 4-diamino phenoxy)-the third-1; 2-glycol, 2-[2-amino-4-(methylamino)-phenoxy group] ethanol, 2-[(5-amino-2-ethyoxyl-phenyl)-(2-hydroxyethyl)-amino]-ethanol, 2-[(3-aminophenyl) amino] ethanol, N-(2-amino-ethyl) benzene-1; 3-diamidogen, 4-{ [(2,4-diaminourea-phenyl) oxo] methoxyl group }-benzene-1,3-diamidogen and 2; 4-dimethoxy benzene-1, the 3-diamidogen;
M-aminophenol; For example: 3-amino-phenol, 2-(3-hydroxy-4-methyl-phenyl amino)-acetamide, 2-(3-hydroxyl-phenyl amino)-acetamide, 5-(2-hydroxyethylamino)-2-methylphenol, 5-amino-2; 4-chlorophenesic acid, 5-amino-2-methyl phenol, 3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol, 5-amino-2-(2-hydroxyl-ethyoxyl)-phenol, 2-chloro-5-(2; 2; 2-three fluoro-ethylaminos)-phenol, 5-amino-4-chloro-2-methyl-phenol, 3-cyclopenta amino-phenol, 5-[(2-hydroxyethyl) amino]-4-methoxyl group-2-methylphenol, 5-amino-4-methoxyl group-2-methylphenol, 3-(dimethylamino) phenol, 3-(diethylamino) phenol, 5-amino-4-fluoro-2-methylphenol, 5-amino-4-ethyoxyl-2-methylphenol, 3-amino-2; 4-two chloro-phenol, 3-[(2-methoxy ethyl) amino] phenol, 3-[(2-hydroxyethyl) amino] phenol, 5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol, 5-[(3-hydroxypropyl) amino]-2-methylphenol, 3-[(3-hydroxy-2-methyl phenyl)-amino] the third-1,2-two pure and mild 3-[(2-hydroxyethyl) amino]-2-methylphenol; With
Hete rocyclic derivatives, for example: 3,4-dihydro-2H-1,4-benzoxazinyl-6-phenol, 4-methyl-2-phenyl-2; 4-dihydro-3H-pyrazoles-3-ketone, 6-methoxy quinoline-8-amine, 4-picoline-2,6-diphenol, 2,3-dihydro-1,4-benzo dioxin-5-phenol, 1; 3-benzo dioxolanes-5-phenol, 2-(1,3-benzo dioxolanes-5-base is amino) ethanol, 3,4-lutidines-2,6-glycol, 5-chloropyridine-2; 3-glycol, 2,6-dimethoxy-pyridine-3,5-diamidogen, 1,3-benzo dioxolanes-5-amine, 2-{ [3; 5-diaminourea-6-(2-hydroxyl-ethyoxyl)-pyridine-2-yl] oxo }-ethanol, 1H-indole-4-alcohol, 5-are amino-2,6-dimethoxy-pyridine-3-alcohol, 1H-indole-5,6-glycol, 1H-indole-7-alcohol, 1H-indole-5-alcohol, 1H-indole-6-alcohol, 6-bromo-1,3-benzo dioxolanes-5-alcohol, 2-aminopyridine-3-alcohol, pyridine-2; 6-diamidogen, 3-[(3,5-diamino-pyridine-2-yl) oxo] the third-1,2-glycol, 5-[(3; 5-diamino-pyridine-2-yl) oxo] penta-1,3-glycol, 1H-indole-2,3-diketone, indoline-5; 6-glycol, 3,5-dimethoxy-pyridine-2,6-diamidogen, 6-methoxypyridine-2; 3-diamidogen and 3,4-dihydro-2H-1,4-benzoxazinyl-6-amine.
Be appreciated that; Coupling agent chemical compound and main intermediate chemical compound comprise the The compounds of this invention that meets chemical formula (1), (1-B), (1-C) and (5) structure, when they are alkali; Form that can free alkali is used; Perhaps with they and organic acid or mineral acid for example the form of the physiological compatibility salt that forms of hydrochloric acid, citric acid, acetic acid, tartaric acid or sulphuric acid use, perhaps when they have aromatics OH group, the for example form use of alkali metal phenolate of salt that can form with alkali.
The total amount of dyestuff former (main intermediate and the coupling agent chemical compound that for example comprise this invention chemical compound) in this invention hair colouring compositions is generally about 0.002% to about 20% weight by the gross weight agent of said hair colouring compositions; Preferred about 0.04% to about 10% weight, and most preferably from about 0.1% to about 7.0% weight.Main intermediate and coupling agent chemical compound use with equimolar amounts usually.Yet, can use main intermediate chemical compound excessive or in shortage, promptly the mol ratio of main intermediate and coupling agent usually at about 5: 1 to about 1: 5 scope.
The hair colouring compositions of this invention will comprise the main intermediate of this invention and the combination of coupling agent with effective tinctorial yield.Main intermediate and be generally about 0.001% to about 10% weight by the weight of said hair dye composition with coupling agent content separately, preferred about 0.01% to about 5.0% weight.When existing, other coupling agent typical case exists with certain amount, makes that the total concentration of coupling agent in said compositions is about 0.002% to about 10% weight, and preferred about 0.01% to about 5.0% weight.When existing, other main intermediate exist with effective colour saturation, and its concentration is generally about 0.001% to about 10.0% weight by the weight of said hair dye composition, and preferred about 0.01% to about 5.0% weight.The remainder of hair dye composition comprises the carrier or the vehicle of coupling agent and main intermediate, and comprises the various adjuvant that are described below.
D.
Suitable carrier
Can use the carrier or the vehicle of any suitable, be generally aqueous solution or water-alcohol solution, be preferably aqueous solution.Carrier or vectorial content usually greater than 80% weight, are typically 90% to 99% weight, preferred 94% to 99% weight by the weight of said hair dye composition.Hair coloring compositions of the present invention can comprise one or more following materials as adjuvant: cationic surfactant, anion surfactant, amphoteric surfactant or zwitterionic surfactant, and spice, antioxidant is ascorbic acid, TGA or sodium sulfite for example; Chelating agen and sequestering agent such as EDTA, thickening agent, basifier or acidulant; Solvent, diluent, inert substance; Dispersant; Penetrating agent, defoamer, enzyme and other dye substance (for example synthetic direct dyes and natural dye).These adjuvant are the cosmetics additive compositions that are usually used in the hair coloring compositions.
Through being mixed with suitable oxidant, hair dye composition of the present invention uses them.Said oxidant and hair dyes precursors reaction make the hair dyes colour developing.Any suitable oxidant all can be used in the hair dyes product composition of this invention, especially hydrogen peroxide (H
2O
2) or its precursor.Urea peroxide, persulfuric acid alkali metal salt, perboric acid alkali metal salt and percarbonic acid alkali metal salt (especially sodium salt) and tripolycyanamide peroxide also suit.Usually with the Aquo-composition form that is commonly referred to as reagent composition oxidant is provided.Said reagent composition normally provides as the independent component in the hair dyes finished product, and is placed in the independent container.Said reagent composition can also comprise the required various compositions of formation reagent composition on compatibility; Be that peroxide stabiliser, foam form agent etc.; And can mix one or more above-mentioned adjuvant, for example surfactant, thickening agent, pH regulator agent etc.Hair coloring compositions is being mixed with color composition with after forming the hair dyes product composition; When being applied to said compositions on the hair; By the hair dyes product composition adjuvant is provided, to realize required product property, for example pH, viscosity, rheological charactristics etc.
Like the form of hair dyes product composition of the present invention can be for example solution, especially aqueous solution or water-alcohol solution.Yet preferred form is thick liquid, cream, gel or emulsion, and its composition is dyestuff composition and the mixture that is suitable for the conventional cosmetics additive component of particular formulations.
E.
Annexing ingredient
Thereby the suitable conventional cosmetics additive component that is used for hair dye composition and reagent composition and is used for this invention hair dyes product composition is described below, and can uses said one-tenth to assign to obtain the required characteristic of hair dye composition, reagent composition and hair dyes product composition.
Solvent: except water, spendable solvent also has low-level chain triacontanol (like ethanol, propanol, isopropyl alcohol, benzylalcohol) and polyol (like carbitol, propylene glycol, hexanediol, glycerol).Through suitable processing, higher alcohol is C8 to C18 aliphatic alcohol for example, especially spermol; Be the organic solvent that suits, precondition is at first through melting the fusing of typical case under low temperature (50 ℃ to 80 ℃); With they liquefaction, mix other then and be generally lipophilic material.
The content of organic solvent in hair dye composition is typically about 5% to about 30% by the weight of said hair dye composition.The content of water is generally about 5% to about 90%, preferred about 15% to about 75% by the weight of said hair dye composition, and most preferably from about 30% to about 65%.
Surfactant: these surfactants are selected from anion surfactant, cationic surfactant, amphoteric surfactant (comprising zwitterionic surfactant) or non-ionic surfactant compound.(cationic surfactant in being included in as the hair-conditioning material usually is hereinafter by independent description) except cationic surfactant, suitable surfactant comprises block polymer, glyceride, phosphate ester, Marlamid and ethoxylated fatty acid ester, alkyl sulfate, ethoxylated alkyl sulfates, alkyl glycerol ether sulfonate, methyl-acyl taurine salt, acyl-hydroxyethyl sulfonate, alkyl ethoxy carboxylate, fatty acid one glycollic amide and the diglycollic amide of aliphatic alcohol sulfate, ethoxylated fatty alcohol sulfate, alkylsulfonate, alkylbenzenesulfonate, alkyl trimethyl ammonium salt, alkyl betaine, ethoxylized fatty alcohol, ethoxylated fatty acid, ethoxylated alkylphenol, ethylene glycol and/or propylene glycol.What be particularly useful is alkyl sodium sulfate and alkylsurfuric acid ammonium, have ether sodium sulfate and the ether ammonium sulfate of 1 to 3 ethylene oxide group and the non-ionic surface active agent of selling with trade name Tergitols (for example C11-C15 palmityl polyoxyethylene ether-9) and Neodols (for example C12-C15 palmityl polyoxyethylene ether-3).Why comprising them is for various reasons, for example in order to help thickening, be used to form emulsion, between hair dyes product composition administration time period, help moistening hair etc.Amphoteric surfactant comprises for example asparagine derivative and betanin, sulfobetaines, glycinate and propionate, and they have and contain 10 alkyl or the alkyl amidos to about 20 carbon atoms of having an appointment.The typical case is applicable to that the amphoteric surfactant of this invention comprises lauryl betaine; Lauroyl both sexes glycinate; Lauroyl both sexes propionate; The lauryl sulfobetaines; The myristyl amido propyl betaine; The myristyl betanin; Stearyl both sexes propyl sulfonic acid salt; The cocoamidoethyl betanin; Cocoamidopropyl; Cocoyl both sexes glycinate; Cocoyl both sexes carboxyl propionate; Cocoyl both sexes carboxyl glycinate; Coco betaine and cocoyl both sexes propionate.
The amount of surfactant in hair dye composition is generally about 0.1% to 30%, preferred 1% to 15% by weight.
Thickening agent: suitable thickening agent comprises high fatty alcohol for example, starch, cellulose derivative, vaseline, liquid paraffin, fatty acid and based on the anion and the nonionic polymeric viscosifier of polyacrylic acid and polyether polyols with reduced unsaturation.Embodiment is the anionic polymer and the non-ionic polymers of hydroxyethyl-cellulose, hydroxy methocel and other cellulose derivative, hydrophobically modified, has especially not only had hydrophilic segment but also has had the above-mentioned polymer (being amphipathic polymer) of hydrophobic part.Useful non-ionic polymers comprises urethane derivative, for example PEG-150/ stearyl alcohol/SDMI copolymer.Suitable polyether urethane is sold by the Rohm & Haas Aculyn
22, Aculyn
44 and Aculyn
46.Other useful amphipathic polymer is disclosed in United States Patent (USP) 6,010, in 541.The embodiment that can be used as the anionic polymer of thickening agent is acrylate copolymer, acrylic ester/ceteth-20 methacrylate copolymer, acrylic ester/ceteth-20 itaconate copolymeric and acrylic ester/mountain Yu base polyoxyethylene ether-25 acrylate copolymer.For association thickener for example Aculyns22, for 44 and 46, said polymer can be included in the hair dyes product hair dye composition or reagent composition both one of in, and surfactant materials is included in another.Therefore, with hair dye composition with after reagent composition mixes, obtained essential viscosity.Amount with certain provides thickening agent, when being administered to product on the hair, the product with suitable viscosity can be provided.The said goods has 1Pa.s (1000cps) usually to the viscosity of 100Pa.s (100000cps) and have the thixotroping rheological behavior usually.
PH regulator agent: be applicable to that the material of regulating hair dye composition pH comprises the basifier for example hydroxide and the carbonate of alkali metal and ammonium; Especially sodium hydroxide and ammonium carbonate; Ammonia, organic amine comprise methylethanolamine, amino methyl propanol, monoethanolamine, diethanolamine and triethanolamine; And acidulant, for example mineral acid and organic acid, for example phosphoric acid, acetic acid, ascorbic acid, citric acid or tartaric acid, hydrochloric acid etc.Referring to US 6,027,538.
Conditioner: suitable conditioning material comprises siloxanes and silicone derivative; Hydrocarbon ils; Quaternary ammonium monomer chemical compound and quaternary ammonium polymer.The quaternary ammonium monomer chemical compound is typically cationic compound, but also comprises betanin and other both sexes and the amphion material that conditioning effect is provided.Suitable quaternary ammonium monomer chemical compound comprises the docosyl tri alkyl ammomium chloride; INCROQUAT TMC-80 ECONOL TM22; Alkyl benzyl dimethyl ammonium bromide or ammonium chloride; Benzyltriethylammoinium chloride; Dihydroxyethyl tallow monomethyl ammonium chloride; The C12-18 dialkyl dimethyl ammonium chloride; Cetalkonium chloride; Cetearyl trimethylammonium bromide and ammonium chloride; Cetyl trimethyl ammonium bromide; Hexadecyltrimethylammonium chloride and cetyl trimethyl methylsulfuric acid ammonium; The cetyl pyridinium chloride; Cocos nucifera oil acylamino-propyl group ethyl dimethyl ethyl ammonium sulfate; Cocos nucifera oil acylamino-propylthio diethyl phthalate; Cocoyl ethyl dimethyl ethyl ammonium sulfate; Cocoyl trimethyl ammonium chloride and ethyl sulfuric acid ammonium; Two mountain Yu base alkyl dimethyl ammonium chloride; Varisoft 432PPG; Two cocoyl alkyl dimethyl ammonium chlorides; The dilauryl alkyl dimethyl ammonium chloride; Two Semen sojae atricolor alkyl dimethyl ammonium chlorides; Ditallow dimethyl ammonium chloride; H-tallow base trimethyl ammonium chloride; Ethoxy cetyl alkyl dimethyl ammonium chloride; The myristyl dimethyl benzyl ammonium chloride; The oil base dimethyl benzyl ammonium chloride; Semen sojae atricolor ethoxyl methyl ethyl sulfuric acid ammonium; The Semen sojae atricolor trimethyl ammonium chloride; Stearyl dimethyl benzyl ammonium chloride and many other chemical compounds.Referring to WO 98/27941.Quaternary ammonium polymer is typically cationic polymer, but also can comprise both sexes and amphoteric ion polymer.Available exemplary polymer is polyquaternary ammonium salt-4, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10, polyquaternary ammonium salt-22, polyquaternium-32, polyquaternium-39, polyquaternium-44 and polyquaternary ammonium salt-47.The siloxanes that is suitable for conditioning hair is polydimethylsiloxane, amino-terminated polydimethylsiloxane, dimethicone copolyol and dimethiconol.For suitable siloxanes, also can be referring to the WO 99/34770 that announced on July 15th, 1999.Suitable hydrocarbon ils comprises mineral oil.
The content of conditioner in said hair dye composition is generally about 0.01% to about 5% by the weight of said compositions.
Direct dyes: also comprise compatible direct dyes like hair colouring compositions of the present invention, comprise disperse that black 9, HC is yellow 2, HC is yellow 4, HC is yellow 15,4-nitro o-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, HC are red 3, disperse violet 1, HC are blue 2, disperse blue 3 and disperse blue 377.The content of these direct dyess in hair colouring compositions of the present invention is about 0.05% to 4.0% by weight.
Natural component: for example, protein and protein derivatives, and vegetable material for example Aloe, Chamomile and Flos Impatientis extract.
Carbanion source and free radical scavenger system: said hair colouring compositions can comprise the system of being made up of carbanion source, carbamic acid radical ion source, bicarbonate ion source and their mixture and free radical scavenger, and said system has enough amounts during coloring process, to reduce the damage to hair.The content of above-mentioned carbanion is typically 0.1% to 15% of said composition weight, and is preferred 0.1% to 10%, and more preferably 1% to 7%, and the content of above-mentioned free radical scavenger is 0.1% to 10%, preferred 1% to 7%.Preferably, free radical scavenger exists with certain amount, so that the ratio of free radical scavenger and carbanion is 1: 1 to about 1: 4.The preferred free radical scavenger of selecting is not so that it is identical component with basifier.
Suitable ion source includes but not limited to: sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, guanidine carbonate, bicarbonate guanidine, lithium carbonate, calcium carbonate, magnesium carbonate, brium carbonate, ammonium carbonate, ammonium bicarbonate, and their mixture.Preferred carbanion source is sodium bicarbonate and potassium bicarbonate.Also preferred ammonium carbonate and ammonium bicarbonate.
Free radical scavenger is to react the carbonate group is transformed into the component of active low component through a series of fast reactions with the carbonate group.Preferably, when free radical scavenger comprised nitrogen-atoms, its pKa that has＞7 were to stop the protonated of nitrogen.Preferred free radical scavenger can be selected from alkanolamine, aminosaccharide, amino acids and their mixture, also can include but not limited to: MEA, 3-amino-1-propanol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 1-amino-2-propanol, 1-amino-2-butanols, 1-amino-2-amylalcohol, 1-amino-3-amylalcohol, 1-amino-4-amylalcohol, 3-amino-2-methyl third-1-alcohol, 1-amino-2-methyl propan-2-ol, 3-amino the third-1; Potassium salt, sodium salt and the ammonium salt of 2-glycol, glycosamine, N-acetyl glucosamine, glycine, arginine, lysine, proline, glutamine, histidine, serine, tryptophan and above-mentioned substance, and their mixture.Other preferred free radical scavenging immunomodulator compounds comprises benzylamine, glutamic acid, imidazoles, di-tert-butyl hydroxy toluene, hydroquinone, catechol and their mixture.
Other adjuvant comprises polysaccharide, alkyl polyglycoside, buffer agent, chelating agen and sequestering agent, antioxidant and peroxide stabiliser, those described in WO 01/62221.
But preceding text are mentioned the not concrete suitable adjuvant of confirming and are listed in the Cosmetics by The; Toiletry is among the International Cosmetics IngredientDictionary and Handbook (the 8th edition) that and Fragrance Association publishes.Special in the 2nd volume, the 3rd part (chemical classes) and the 4th part (function) are used for confirming that concrete adjuvant is to realize one or more specific purposes.
Above-mentioned conventional cosmetic composition uses with the amount that is suitable for its functional purpose.For example; Surfactant concentrations content as wetting agent, association agent and emulsifying agent is generally about 0.1% to 30% by weight; The consumption of thickening agent is about 0.1% to 25% by weight, and the concentration of used hair-care functional mass is typically about 0.01% to 5.0% by weight.
In the time of on being administered to hair, promptly as hair dye composition of the present invention with after developer mixes, the coloring hairs product composition can be faintly acid, neutrality or alkaline according to their composition.It is about 6 to 11.5 that hair dye composition can have, and preferred about 6.8 to about 10, and especially be about 8 to about 10 pH value.The pH of reagent composition is typically acidity, and pH is generally about 2.5 to about 6.5, is generally about 3 to 5.Can use aforesaid pH regulator agent, regulate the pH of hair dye composition and reagent composition.
F.
Method for using
In order to use hair coloring compositions to come dyed hair, the hair coloring compositions with the invention described above before being about to use mixes with oxidant, and the mixture of capacity is administered on the hair.According to the amount of hair, its consumption is generally about 60 to 200 grams.According to the character of composition, possible interaction etc., some adjuvant that preceding text are listed (for example thickening agent, conditioner etc.) can provide in dye composite or reagent composition or the two, and this is well-known in the art.
Typically, the aqueous solution form that the additive compound of hydrogen peroxide or itself and urea, tripolycyanamide, sodium borate or sodium carbonate can 3% to 12%, preferred 6% is as oxidant, so that the hair dyes colour developing.When with 6% hydrogenperoxide steam generator during as oxidant, the weight rate of hair coloring compositions and reagent composition is 5: 1 to 1: 5, but preferred 1: 1.
Usually, preparation comprises the hair colouring compositions of main intermediate and coupling agent, and mixes with the reagent composition that comprises oxidant in use, to obtain the compositions (hair dyes product composition) of uniform, preferred thickening basically.After being prepared as follows, the coloring hairs product composition is administered on the hair to be dyed, and keep in touch with hair necessarily can be effectively with the chromotrichial time.Under about 15 ℃ to 50 ℃, make said hair dyes product composition on said hair, act on about 2 to about 60 minutes, preferred about 15 to 45 minutes, especially about 30 minutes.Thereafter, water flushing hair to be removing the coloring hairs product composition, and dry.If necessary, shampoo is washed hair and flushing, for example for example citric acid or tartaric acid solution flushing and dry of water or weakly acidic solution.Also can choose the conditioning products that provides independent wantonly.
G.
Coloring hairs product cover box
Hair dye composition and reagent composition are formed for the system of dyed hair jointly.Said system can be used as the cover box and provides, and it comprises separately independent hair dye composition, developer, optional conditioner or other hair treatment product container and operation instruction in the packing at one.
H.
Non-limiting example
The combination of the main intermediate that this invention is particularly useful and coupling agent will provide have the excellent color fastness, fastness to washing, rub resistance degree and good coloured composition optionally.
When making N-phenyl-benzene-1,3-diamidogen and 2-(4,5-diaminourea-pyrazol-1-yl)-when ethanol combines to come to the forehead chromotrichia; Said hair is by purple, and when making N-(4-amino-phenyl)-pyridine-2,6-diamidogen and 2-(4; 5-diaminourea-pyrazol-1-yl)-when ethanol combines to come to the forehead chromotrichia; Said hair is dyed blueness, and when making N-methyl-benzene-1,3-diamidogen or benzene-1; When the 3-diamidogen combined with identical pyrazoles main intermediate dyestuff, said hair was dyed kermesinus and redness respectively.
Compare with the hair colouring compositions that is closely related, the superior character of this invention hair colouring compositions can be explained by following test.
Painted embodiment 1
Combinations thing shown in the table 1 can be used for to the forehead coloring hairs.The hydrogen peroxide of the said colouring compositions of 100g with 100g 20 volumes mixed.The gained mixture is administered on the hair, and itself and hair were kept in touch 30 minutes.Shampoo is washed painted hair then, the water flushing, and dry.The scope of ingredients listed is the exemplary usable concentration at material described in the hair dyes product in the table 1.
Table 1
The compositions that is used for dyed hair
1Generally, these compositions are by weight in 2% to 15% scope.
Dyeing embodiment 2
Use the forehead hair of heavy 700mg to 900mg.Use combination thing A (of the present invention), B (comparison), C (comparison) and the D (of the present invention) shown in the table 2 to come to the forehead chromotrichia.The hydrogen peroxide of 100g hair colouring compositions with 100g 20 volumes mixed.The gained mixture is administered on the hair, and make its about 20 ℃ down and hair kept in touch 30 minutes.Shampoo is washed institute's dyeing hair then, and water flushing and dry.Use derives from the Minolta spectrophotometer CM-3700d of Minolta Co..Color space is CIE L
*a
*b
*, and light source is the D65 daylight with 10 ° of viewers.Color space L
*Be meant brightness, and a
*And b
*It is chromaticity coordinate.+ a is a red direction, and-a is green direction, and+b is yellow direction, and-b is blue direction.Total variation of color is represented that by Δ E wherein Δ E is defined by following formula:
Acid antiperspirant method of testing
One lock of hair that will dye color places the wide mouthed bottle that comprises the 60ml acid antiperspirant solution that is described below, and 40 ℃ of held 18 hours.Measure to obtain CIE L then with this lock of hair flushing, drying, and with MinoltaCM-3700d
*a
*b
*Repeat this method under the same conditions, a lock of hair placed the solution that has just prepared, placed once more 18 hours, and will wash once more, dry and measure this lock of hair.
Acid antiperspirant solution is by the 10g sodium chloride, 1g lactic acid (USP 85%), the 1g ADSP (Na that are dissolved in the 1L distilled water
2HPO
4) and 0.25g (+) histidine one hydrochlorate composition.
Table 2:
Table 3. derives from the CIE L of compositions A, B, C and D
*a
*b
*Value
Can notice: N-phenyl-benzene-1; 3-diamidogen and 2-(4; 5-diaminourea-pyrazol-1-yl)-ethanol combines can be with forehead hair purple (compositions A); And N-methyl-benzene-1,3-diamidogen (compositions B) or benzene-1,3-diamidogen (compositions C) combines and can respectively hair be dyed kermesinus and redness with identical pyrazoles main intermediate.In addition, compositions A-b
*Value is for-16.75, be respectively-3.49 with-4.93 compositions B and C-b
*Value forms contrast.
According to table 3, institute's dyeing hair shows the toleration of sour antiperspirant influence: with comprise N-methyl-benzene-1, the compositions B of 3-diamidogen or comprise benzene-1, the compositions C of 3-diamidogen compares, and comprises N-phenyl-benzene-1, the compositions A of 3-diamidogen shows better color fastness.Test after 36 hours, the total color difference of compositions A (Δ E) is merely 5.76, and the Δ E of compositions B and compositions C then is respectively 25.87 and 22.93.
Be also noted that N-(4-amino-phenyl)-pyridine-2,6-diamidogen and 2-(4; 5-diaminourea-pyrazol-1-yl)-the ethanol combination; Can the forehead hair be dyed blueness (compositions D), and as stated, compositions B and compositions C then dye kermesinus and redness with hair respectively.Compositions D-b
*Value is for-10.89, be respectively-3.49 with-4.93 compositions B and C-b
*Value forms contrast.
According to table 3, institute's dyeing hair shows the toleration of sour antiperspirant influence, compares with compositions B or compositions C, comprises N-(4-amino-phenyl)-pyridine-2 equally, and the compositions D of 6-diamidogen shows better color fastness.Test after 36 hours, the total color difference of compositions D (Δ E) is merely 4.08, and the Δ E value of compositions B and compositions C then is respectively 25.87 and 22.93.
Therefore, compare with the hair colouring compositions that is closely related, hair colouring compositions of the present invention shows to have superior characteristic on to the toleration of sour antiperspirant.
The relevant portion of all references document is all introduced the present invention for your guidance in detailed Description Of The Invention.Quoting of any document is unintelligible for being to its approval as prior art of the present invention.
Although explained and described the present invention with specific embodiments, it would be obvious to those skilled in the art that and under the situation that does not deviate from the spirit and scope of the present invention, can make many other change and modifications.Therefore, in additional claims, comprise all these variations and the modification that belongs in the scope of the invention consciously.
Claims (4)
1. hair colouring compositions, said compositions comprises:
A) at least a coupling agent, wherein said coupling agent are to be selected from the group of being made up of following material: N-(4-amino-phenyl)-pyridine-2,6-diamidogen, N-(5-amino-pyridine-2-yl) pyridine-2; 6-diamidogen, N-(5-aminopyridine-2-yl) benzene-1,3-diamidogen, N-(4-pyrrolidine-1-base-phenyl)-pyridine-2,6-diamidogen, N-(4-amino-phenyl)-N '-methyl-pyridine-2; 6-diamidogen, 2-[4-(6-methylamino-pyridine-2-base is amino)-phenyl amino]-ethanol, 2-[6-(4-amino-phenyl amino)-pyridine-2-base is amino]-ethanol, N-(4-amino-phenyl)-N-methyl-pyridine-2,6-diamidogen, N-(1H-pyrroles-2-yl)-pyridine-2,6-diamidogen, N-(6-amino-pyridine-2-yl)-pyrimidine-2; 4,5, (5-amino-[1 for 6-tetramine, N-; 3,4] thiadiazoles-2-yl)-and pyridine-2,6-diamidogen, N3-(4-aminophenyl) pyridine-3; 5-diamidogen, N3-(4-aminophenyl)-N5-(2-hydroxyethyl) pyridine-3,5-diamidogen, N3-(thiazol-2-yl) pyridine-3,5-diamidogen, N2-(4-aminophenyl) pyridine-2; 4-diamidogen, N2-(4-aminophenyl)-5-chloropyridine-2,6-diamidogen, N2-(4-aminophenyl)-5-methoxypyridine-2,6-diamidogen, N3-(4-aminophenyl)-N3-picoline-3; 5-diamidogen, N3-(5-aminopyridine-2-yl) pyridine-3,5-diamidogen, N3-(4,5; 6-Triaminopyrimidine-2-yl) pyridine-3,5-diamidogen, N2-(4-aminophenyl)-N2-picoline-2,4-diamidogen, N4-(4-aminophenyl)-N4-picoline-2; 4-diamidogen, N2-(4-aminophenyl)-3-chloropyridine-2; 6-diamidogen and N2-(4-aminophenyl)-3-Methoxy Pyridine-2, the 6-diamidogen
B) at least a main intermediate, said main intermediate are 2-(4,5-diaminourea-pyrazol-1-yl)-ethanol; With
C) carrier that suits.
2. hair colouring compositions as claimed in claim 1, said compositions also comprise one or more annexing ingredients that is selected from the group of being made up of following material: auxiliary coupling agent, auxiliary main intermediate, direct dyes, oxidant, thickening agent, pH regulator agent, conditioning material and carbanion source and free radical scavenger system.
3. the method for a dyed hair said method comprising the steps of:
A) use hair colouring compositions according to claim 1 or claim 2 to said hair; With
B) water washes said hair.
4. coloring hairs product that overlaps box form, said product comprises:
A) the first independent container of hair colouring compositions according to claim 1 or claim 2 is housed; With
B) the second independent container of oxidizing agent composition is housed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/077,744 | 2005-03-11 | ||
| US11/077,744 US7303592B2 (en) | 2002-03-04 | 2005-03-11 | Hair coloring compositions for use in oxidative hair dyeing |
| PCT/US2006/008559 WO2006099115A2 (en) | 2005-03-11 | 2006-03-10 | Hair coloring compositions for use in oxidative hair dyeing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101137345A CN101137345A (en) | 2008-03-05 |
| CN101137345B true CN101137345B (en) | 2012-10-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800079426A Expired - Fee Related CN101137345B (en) | 2005-03-11 | 2006-03-10 | Hair coloring compositions for use in oxidative hair dyeing |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7303592B2 (en) |
| EP (3) | EP1982748A3 (en) |
| JP (1) | JP4685153B2 (en) |
| CN (1) | CN101137345B (en) |
| MX (1) | MX2007010622A (en) |
| WO (1) | WO2006099115A2 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7303592B2 (en) | 2002-03-04 | 2007-12-04 | The Procter & Gamble Company | Hair coloring compositions for use in oxidative hair dyeing |
| US8003583B2 (en) * | 2005-12-21 | 2011-08-23 | Chevron Oronite Company Llc | Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions |
| FR2925304B1 (en) * | 2007-12-20 | 2016-03-11 | Oreal | COMPOSITION COMPRISING ALKANOLAMINE, BASIC AMINO ACID AND ADDITIONAL ALKALINE AGENT SUITABLE FOR SELECTION |
| FR2925318B1 (en) * | 2007-12-20 | 2010-01-08 | Oreal | COMPOSITION COMPRISING AN ALKANOLAMINE, AN AMINO ACID AND AN ASSOCIATIVE POLYMER. |
| FR2925305B1 (en) * | 2007-12-20 | 2010-01-08 | Oreal | COMPOSITION COMPRISING ALKANOLAMINE, AMINO ACID AND CATIONIC POLYMER |
| JP5839200B2 (en) * | 2010-08-31 | 2016-01-06 | 日産化学工業株式会社 | Diamine |
| CN103379894B (en) * | 2011-02-22 | 2016-11-02 | 宝洁公司 | Comprise 1-hexyl/heptyl-4,5-diamino-pyrazole and 1,3-phenylenediamine and the oxidative dye compositions of derivant thereof |
| US8366791B1 (en) | 2011-09-02 | 2013-02-05 | Warner Babcock Institute | Formulation and method for hair dyeing |
| US8828100B1 (en) | 2013-10-14 | 2014-09-09 | John C. Warner | Formulation and processes for hair coloring |
| DE102014215483A1 (en) * | 2014-08-06 | 2016-02-11 | Henkel Ag & Co. Kgaa | "New oxidation dye precursors of the oxy, thio and aza-bisbenzene type" |
| DE102014215485A1 (en) * | 2014-08-06 | 2016-02-11 | Henkel Ag & Co. Kgaa | "New oxidation dye precursors of the oxy, thio and aza-bisbenzene type" |
| DE102014215484A1 (en) * | 2014-08-06 | 2016-02-11 | Henkel Ag & Co. Kgaa | "New oxidation dye precursors of the oxy, thio and aza-bisbenzene type" |
| KR102162502B1 (en) | 2017-05-22 | 2020-10-06 | 주식회사 엘지화학 | Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent comprising the same, and liquid crystal aligning film, liquid crystal display device using the same |
| KR102020030B1 (en) | 2017-08-24 | 2019-09-10 | 주식회사 엘지화학 | Polymer for liquid crystal aligning agent, amd liquid crystal aligning agent composition comprising the same, and liquid crystal aligning film, liquid crystal display device using the same |
| KR102235476B1 (en) | 2018-03-30 | 2021-04-01 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
| US11351106B2 (en) * | 2020-09-14 | 2022-06-07 | Milliken & Company | Oxidative hair cream composition containing thiophene azo colorant |
| US20220362122A1 (en) * | 2021-04-01 | 2022-11-17 | Elc Management Llc | Hair Treatment Compositions With Amine Derivatives |
| WO2023163906A1 (en) * | 2022-02-25 | 2023-08-31 | Henkel Ag & Co. Kgaa | Oxidative dyeing agent for keratin fibers comprising novel dye precursor combinations |
| US11730694B1 (en) * | 2022-05-25 | 2023-08-22 | L'oreal | Hair coloring compositions and methods |
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| DE1218116B (en) * | 1963-04-19 | 1966-06-02 | Schwarzkopf Fa Hans | Preparations for coloring living hair |
| DE3728748A1 (en) | 1987-08-28 | 1989-03-09 | Henkel Kgaa | Hair Dye |
| DE3741236A1 (en) * | 1987-12-05 | 1989-06-15 | Henkel Kgaa | PHENYLAMINO AND PHENYLAMINOMETHYL-PYRIDINES AND HAIR AGENTS CONTAINING THEM |
| DE3843892A1 (en) * | 1988-12-24 | 1990-06-28 | Wella Ag | OXIDATION HAIR AGENTS CONTAINING DIAMINOPYRAZOL DERIVATIVES AND NEW DIAMINOPYRAZOLE DERIVATIVES |
| DE4422603A1 (en) | 1994-06-28 | 1996-01-04 | Wella Ag | Agent for oxidative dyeing of hair based on 4,5-diaminopyrazoles and m-phenylenediamine derivatives |
| FR2751533B1 (en) | 1996-07-23 | 2003-08-15 | Oreal | COMPOSITION OF OXIDIZING DYE FOR KERATINIC FIBERS CONTAINING A NON-IONIC AMPHIPHILIC POLYMER |
| US6554871B2 (en) | 1996-10-18 | 2003-04-29 | Wella Ag | Oxidative hair dye precursor compositions containing 4-5-diaminopyrazole, 5-amino-2-methylphenol and m-phenylenediamine compounds and method of dyeing hair |
| GB9626711D0 (en) | 1996-12-23 | 1997-02-12 | Procter & Gamble | Hair colouring compositions |
| FR2767475A1 (en) | 1997-08-25 | 1999-02-26 | Oreal | Oxidation hair dyes |
| FR2773070B1 (en) | 1997-12-31 | 2000-06-30 | Oreal | COMPOSITIONS FOR THE TREATMENT OF KERATINIC MATERIALS COMPRISING THE COMBINATION OF A ZWITTERIONIC POLYMER AND A NON-VOLATILE AND WATER INSOLUBLE SILICONE |
| US6564871B1 (en) * | 1999-04-30 | 2003-05-20 | Smith International, Inc. | High pressure permanent packer |
| DE29909427U1 (en) | 1999-05-29 | 1999-07-22 | Wella Ag | Means for coloring keratin fibers |
| GB0004413D0 (en) | 2000-02-24 | 2000-04-12 | Procter & Gamble | Pretreatment for hair coloring compositions and methods |
| DE10103160A1 (en) | 2001-01-25 | 2001-11-29 | Henkel Kgaa | New and known hair dyes containing m-phenylenediamines give good results, especially with 2,4,5,6-tetraaminopyrimidine as developer |
| US6887280B2 (en) * | 2002-03-04 | 2005-05-03 | The Procter & Gamble Company | Hair coloring compositions for use in oxidative hair dyeing |
| US7303592B2 (en) | 2002-03-04 | 2007-12-04 | The Procter & Gamble Company | Hair coloring compositions for use in oxidative hair dyeing |
| DE20206274U1 (en) | 2002-04-20 | 2002-08-14 | Wella Ag | 2,3-diaminophenol derivatives and oxidation hair colorants containing these compounds |
| DE10245426A1 (en) * | 2002-09-27 | 2004-04-08 | Henkel Kgaa | New coupler components |
| FR2856293B1 (en) * | 2003-06-19 | 2005-08-26 | Oreal | TINCTORIAL COMPOSITION COMPRISING 4,5-DIAMINO-1- (B-HYDROXYETHYL) -1H-PYRAZOLE AS OXIDATION BASE AND 2,6-BIS- (B-HYDROXYETHYL) -AMINO-TOLUENE AS A COUPLER |
-
2005
- 2005-03-11 US US11/077,744 patent/US7303592B2/en not_active Expired - Lifetime
-
2006
- 2006-03-10 EP EP08160558A patent/EP1982748A3/en not_active Withdrawn
- 2006-03-10 JP JP2008500959A patent/JP4685153B2/en not_active Expired - Fee Related
- 2006-03-10 EP EP06737711A patent/EP1855644A2/en not_active Withdrawn
- 2006-03-10 EP EP08160560.2A patent/EP1982749B1/en not_active Revoked
- 2006-03-10 WO PCT/US2006/008559 patent/WO2006099115A2/en active Application Filing
- 2006-03-10 MX MX2007010622A patent/MX2007010622A/en active IP Right Grant
- 2006-03-10 CN CN2006800079426A patent/CN101137345B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 第22页第1段. |
Also Published As
| Publication number | Publication date |
|---|---|
| US7303592B2 (en) | 2007-12-04 |
| EP1982748A3 (en) | 2008-11-12 |
| JP4685153B2 (en) | 2011-05-18 |
| MX2007010622A (en) | 2007-10-08 |
| JP2008537932A (en) | 2008-10-02 |
| EP1982749A2 (en) | 2008-10-22 |
| EP1982749B1 (en) | 2013-04-17 |
| US20050188480A1 (en) | 2005-09-01 |
| WO2006099115A2 (en) | 2006-09-21 |
| CN101137345A (en) | 2008-03-05 |
| EP1982749A3 (en) | 2008-11-12 |
| WO2006099115A3 (en) | 2006-12-21 |
| EP1855644A2 (en) | 2007-11-21 |
| EP1982748A2 (en) | 2008-10-22 |
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